Photographic materials for the silver dye bleach process

ABSTRACT

The provision in a light-sensitive silver-dye-bleach silver halide emulsion of a bis-azo dye which is a light fast yellow dye compatible with photographic layers to provide uniform distribution and having brilliant spectral properties by resisting side absorption.

United States Patent [72] Inventors Hans Vetter Cologne, Stammheim; Karl-Heinz Freytag, Leverkusen; Justus Danhauser, Cologne, Stammheim; Erich Bockly, Leverkusen, all of Germany [21] Appl. No. 778,294

[22] Filed Nov. 22, 1968 [45] Patented Oct. 26, 1971 [7 3] Assignee AGFA-Gevaert Aktiengesellschaft Leverkusen, Germany [32] Priority Dec. 13, 1967 [33] Germany [54] PHOTOGRAPIIIC MATERIALS FOR THE SILVER [51] Int.Cl G03c l/40 3,259,498 7/1966 Anderau et a1. 96/99 3,455,695 7/1969 Piller 96/99 3,467,522 9/1969 Freytag et a1. 96/99 3,480,438 1 1/1969 Freytag et al.. 96/99 3,482,979 12/1969 Skoog 96/99 Primary Examiner-William D. Martin Assistant Examiner-Theodore G. Davis Attorney-Connolly and Hutz ABSTRACT: The provision in a light-sensitive silver-dyebleach silver halide emulsion of a bis-azo dye which is a light fast yellow dye compatible with photographic layers to provide uniform distribution and having brilliant spectral properties by resisting side absorption.

PHOTOGRAPHIC MATERIALS FOR THE SILVER DYE BLEACH PROCESS This invention relates to color photographic materials for the silver-dye-bleach process which materials contain particularly light-fast yellow azo dyes.

It is known that color photographic images can be produced by the silver-dye-bleach process, wherein a dye, usually an azo dye, is bleached in a homogeneously dyed colloid layer in accordance with a silver image which had been produced photographically.

lt is possible to produce both negative and reversal silverdye-bleach images. If it is desired to produce positive paper prints or duplicate positives from diapositives, the silver image is produced by means of a simple black-and-white development, this silver image representing a negative of the copying original. Since the image dye which is homogeneously distributed in the layer (or in the three layers of a multicolor material) is bleached proportionately to the silver image a dye image is obtained, which is positive with respect to the original. If a silver image is produced which is positive with respect to the original, for example, by a blackand-white reversal development or by the bromide ion diffusion method or silver salt diffusion method, then after the color bleaching a dye image is formed which is opposite in gradation to the original, that is to say a positive color image is formed if the original is a negative color image.

The standards set as regards dyes for the process described are particularly high, since these dyes must be spectrally suitable, and should also be easily bleachable and fast to light.

Furthermore, they must be completely resistant to diffusion in the gelatin which is almost exclusively used as layer former. Excellent light fastness is of particular importance but resistance to acid gases such as occur in the atmosphere in industrial areas, and high brilliance, i.e. freedom from side absorption in undesired spectral regions combined with suitable spectral position of the absorption, are also of importance.

It is among the objects of the invention to provide yellow azo dyes which are easily to prepare, are compatible with the photographic layers, and have spectral properties which satisfy the various requirements of the silver-dye-bleach process.

The above objects have been attained by providing a yellow bis-diazo dye of the following formula:

wherein R,=( 1) hydrogen, (2) an alkyl group with preferably up to three carbon atoms, (3) halogen such as chlorine or bromine, (4) an alkoxy group with preferably up to three carbon atoms, (5) an acylamino group in which the acyl groups are advantageously derived from aliphatic monoor dicarboxylic acids which have up to six carbon atoms or from benzene carboxylic acids, especially benzoic acid, or (6) an ureido group;

R hydrogen, an alkyl or alkoxy group having preferably up to three carbon atoms or halogen such as chlorine or bromine;

X (i) carbonyl, (2) an acyl group derived from a saturated or olefinically unsaturated aliphatic dicarboxylic acid having preferably up to 12 carbon atoms, such as Jhe following dyes have proved to be especially suitable:

I NH

The dyes which are to be used according to the invention are prepared by known methods. For example, the dyes are prepared by first coupling diazotized amino arylsulfonic acids with l-amino-3-acylamino benzene compounds, reference is made to US. Pat No. 3,480,438 columns seven to nine. The resulting amino azo compound is reacted with phosgene or a dicarboxylic acid chloride, such as phthalic acid chloride, or a fumaric acid chloride. Reference is made to column nine of US. Pat. No. 3,480,438 for reaction with phosgene. Reference is made to U.S. Pat. No. 2,813,856 for reaction of amino azo dyes with fumaric acid chloride. Reference is also made to l-louben/Weyl, Methoden der organischen chemie" fourth Edition, Volume X/3 page 398.

A special advantage of these dyes over known dyes of similar constitution is the ease with which they can be made in a particularly pure form so that problems caused by impurities are avoided. The spectral properties, as well as the brilliance of the dyes, are excellent. Because of the outstanding compatibility with silver halide gelatin emulsions the dyes can be easily incorporated in the layers and a very unifonn distribution of the dyes is thus achieved. Many other azo dyes which are spectrally suitable are inoperative because they are unsatisfactory in respect of the latter properties. I

On account of their excellent properties, the dyes according to the invention can be applied in color photographic layers for the silver-dye-bleach process in various ways. As will be seen from the following examples, they are preferably employed as image dyes in layers which are subjected to a simple black-and-white development and thus form in the subsequent dye bleaching bath in a direct positive dye image. However, it is also possible to carry out a black-and-white reversal development, whereby after treatment with common dyebleaching baths, dye images with a gradation opposite to the original are obtained.

The dyes are substantially inert to agents customarily added to photographic layers, such as stabilizers, sensitizing dyes, chemical sensitizers, plasticizers, wetting agents, hardeners and the like.

As shown in the following example, they can be bleached out to pure whites in different types of bleaching baths, such as those which are based on quinoline and iodide, as described in US. Pat. No. 2,629,568 (example 29) or thiourea (as indicated in British Pat. No. 507,211) and with different bleaching catalysts, such as quinoxalines or phenazine derivatives.

They can be applied onto any suitable supports, such as glass, baryta-coated papers, papers of all types which have been made water repellent, such as polyethylene-coated papers, cellulose acetate or polyesters and polycarbonate films and pigmented cellulose acetate films.

The image whites are also not discolored by exposure to light over long periods.

EXAMPLE I 400 ml. of a 4 percent gelatin solution containing 4.5 g. of dye l and 0.7 g. of saponin, are added to 800 ml. of a melted silver bromide gelatin emulsion. After the addition of 20 ml. of a 1 percent aqueous solution of tris-acryloylhexahydrotriazine as hardening agent one sample of the emulsion is applied onto a support of baryta-coated paper and another on to a support of cellulose triacetate in a thickness which corresponds to a silver application of 0.6 to 0.9 g. of silver per m A strip of each of the dried materials is exposed in a sensitometer customarily employed in the art behind a grey step wedge, using yellow or white light. The exposed samples are processed as follows:

1. Development: 5 minutes in the following developer solution:

p-methylaminophenol hydro uinone 3 g. anhydrous sodium sulfile 13 g. sodium bromide l g. anhydrous soda 26 g.

water to 1,000 ml.

2. Rinsing: 5 minutes.

water up to L000 ml.

4. Rinsing: 5 minutes.

5. Hardening: 5 minutes in the following bath:

formaldehyde (30% aqueous solution) sodium bicarbonate water up to L000 ml.

I00 ml 6. Rinsing: 5 minutes 7. Dye bleaching: 15 minutes in the following bath:

potassium iodide 10 g.

sodium hypophosphite l0 g.

sulfuric acid conc. 75 ml.

quinoline water up to 1,000 ml.

8. Rinsing: 5 minutes.

9. Bleach fixing: 10 minutes in the following bath:

tetrasodium methylene diamine water up to 800 ml.

10. Final rinsing: 15 minutes.

After drying, pure yellow dye wedges with high brilliance and good whites are obtained. The test wedges show no dye diffusion and have excellent light fastness. The layers are eminently suitable for use in the production of the yellow par tial image in a multilayer photographic material.

EXAMPLE 2 The same procedure is employed as in example 1 but using 4.8 g. of dye 5. After exposure and processing as in example 1, baths one to six, the process is continued as follows:

7. Dye bleaching: minutes in the following bath:

thiourea 28 g.

potassium bromide l8 g.

2-arnino-3-hydroxyphenazine 3 mg. 200 ml.

hydrochloric acid conc. water u to 5,000 ml.

8. Rinsing: 5 minutes. 9. Bleaching: 5 minutes in the following bath:

25 g. ml.

copper chloride hydrochloric acid conc. water up to L000 ml.

10. Fixing: 5 minutes as described in example 1, bath number three. 1 1. Final rinsing: minutes. After drying, a result very similar to that of example 1 is obtained.

EXAMPLE 3 0cm. OCH; OH NHCOQ 80,11 son:

the preparation of which is described in French Pat. No. 1,471,787, dissolved in 200 ml. of a 2 percent gelatin solution which in addition contains 10 ml. of a lpercent aqueous solution of N,N,N"-tris-acryloylhexahydrotriazine as hardener and 0.5 g. of saponin. The silver was applied in a quantity of 0.8 g./m in the form of silver halide.

2. An intermediate layer of 2 percent gelatin solution.

3. A green-sensitive layer which contains, for every 500 ml. of the same silver bromo iodide emulsion, 15 mg. of the sensitizer of example 2 of German Pat. No. 1,177,481 and 2.5 g. of the dye of the following formula:

cmQ-s 01-17111 on the preparation of which is described in German Pat. No. 1,039,840, dissolved in 200 ml. of a 2 percent gelatin solution which in addition contains 10 ml. of a 1 percent aqueous solution of N,N',N"-trisacryloylhexahydrotriazine as hardener as well as 0.4 g. of saponin. The silver is applied in a quantity of 0.75 g./m in the form of the silver halide.

4. An intermediate layer of a 4 percent gelatin solution to which 8 g. of tartrazine areadded per liter.

5. A nonsensitized silver bromide emulsion layer of the type use in example 1.

6. A protective layer of 2 percent gelatin solution.

After drying, the material is exposed behind a multicolored transparency and processed in the manner described in example l, with the difference that the treatment time in the dye bleaching bath is increased to 25 minutes. A color-photographic image in true colors is obtained.

EXAMPLE 5 The procedure is the same as that described in example 4 with the difference that the tartrazine-containing gelatin layer between the green sensitized layer and the nonsensitized emulsion layer is replaced by an arrangement of layers as follows:

1. An intermediate layer ofa 2 percent gelatin solution 2. A filter layer of a 2 percent gelatin solution which contains silver filter yellow having a density of 0.3 for a layer thickness of 1 micron and 0.3 g. of dye 5.

3. An intermediate layer of a 2 percent gelatin solution.

After drying, exposure and processing as described in example 4, a color'photographic image of the original with particularly brilliant color tones is obtained.

We claim:

1. A light-sensitive silver-dye-bleach silver halide emulsion layer containing a bis-azo dye of the following formula:

in which R represents hydrogen, chlorine, bromine alltyl, having up to three carbon atoms, acylamino or an ureido group;

R represents hydrogen, chlorine bromine alkyl having up to three carbon atoms or alkoxy having up to three carbon atoms and X represents carbonyl or the acyl group of a saturated or unsaturated aliphatic dicarboxylic acid or of an aromatic dicarboxylic acid.

2. The light-sensitive emulsion of claim 1, wherein R represents an acylamino group, the acyl radical of which is derived from a saturated or unsaturated monobasic or dibasic aliphatic carboxylic acid which has up to six carbon atoms.

3. The light-sensitive emulsion of claim I, wherein R represents an ureido group.

4. The light-sensitive emulsion of claim 1, wherein X represents carbonyl or acyl derived from a benzene dicarboxylic acid.

5. The light-sensitive emulsion of claim 1, wherein X stands I for acyl derived from an olefinically unsaturated dicarboxylic SO3H acid.

6. The light-sensitive emulsion of claim 4, wherein the bis- I azo dye has the followingformula: 5 H,N-C 0 10. The light-sensitive emulsion of claim 5, wherein the bis- Q azo dye has the following formulaz N NE W l 0 N=N NH-C O-CH QQ*' .=9TPQ 3 7. The light-sensitive emulsion of claim 4, wherein the bis- I azo dye has the 9! 1" $9319 3. HOOCCH=CH-CO 1 I\-I=N -NHOO 11. The light-sensitive emulsion of claim 5, wherein the bisazo dye has the following formula: 7 so u r I if o -cn=cH-oo on I HOOC-CH=CH--CO 8. The light-sensitive emulsion of claim 4, wherein the bis- =CH C O NH-N=N azo dye has the following formula: II:H

l 12. The light-sensitive emulsion of claim 4, wherein the bis- 40 azo dye has the following formula:

9. The light-sensitive emulsion of claim 4, wherein the bisazo dye has thefollowing formula: C O-NHQN=N S0=H HO S@N=N NHC O-NH IIIH HOOC-(H'h-CHr-C 0 1711 i i i t 753;? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 5 5 Dated October 26. 1971 Invent0r(5) Hans Vetter 8t 8,].

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 65, the left hand portion of the formula should read as follows: -COGH=CHCO 3 Column 2, line 14 of formula (2) should read as follows; on the middle ring:

Column 3, line 75 of formula (11), the left hand portion of the formula should read as follows:

UU H

Column 6, line 2, delete the word "in";

Column 7, line 2 should read as follows:

-- tetrasodium ethylene diamine Column 7, line 5 after "2.7 g" insert of the dye Column P line 25, "used" instead of use Signed and sealed this (19th day of August 1972.

A u M .FLLETCHEHJR. ROBERT GOT'ISCHALK W111 U1 floor Commissioner of Patents 

2. The light-sensitiVe emulsion of claim 1, wherein R1 represents an acylamino group, the acyl radical of which is derived from a saturated or unsaturated monobasic or dibasic aliphatic carboxylic acid which has up to six carbon atoms.
 3. The light-sensitive emulsion of claim 1, wherein R1 represents an ureido group.
 4. The light-sensitive emulsion of claim 1, wherein X represents carbonyl or acyl derived from a benzene dicarboxylic acid.
 5. The light-sensitive emulsion of claim 1, wherein X stands for acyl derived from an olefinically unsaturated dicarboxylic acid.
 6. The light-sensitive emulsion of claim 4, wherein the bis-azo dye has the following formula:
 7. The light-sensitive emulsion of claim 4, wherein the bis-azo dye has the following formula:
 8. The light-sensitive emulsion of claim 4, wherein the bis-azo dye has the following formula:
 9. The light-sensitive emulsion of claim 4, wherein the bis-azo dye has the following formula:
 10. The light-sensitive emulsion of claim 5, wherein the bis-azo dye has the following formula:
 11. The light-sensitive emulsion of claim 5, wherein the bis-azo dye has the following formula:
 12. The light-sensitive emulsion of claim 4, wherein the bis-azo dye has the following formula: 